Developing analytical or instrumental methods for the purity assessment of poly(amidoamine) dendrimers (PAMAMs) is almost equally important as much as integrating novel synthesis and purification methods to obtain ideal and monodisperse dendrimers. The aim of this study was to investigate the use of chemometric methods; principal component regression (PCR), and partial least squares (PLS2) to assess the purity of PAMAMs. A full factorial experimental design was used to construct PCR and PLS2 calibration models. Absorbance spectra of PAMAMs were collected by UV-Vis spectroscopy between the wavelength ranges of 250-350 nm with 1.00 nm intervals at 101 points. PCR and PLS2 multivariate models were constructed from these full spectra. The built models were compared in terms of prediction powers by means of relative mean square error of prediction values. Validation results of these models provided compelling evidence that PCR and PLS2 models, indeed PLS2 better, could be successively used to predict PAMAM mixtures quantitatively and qualitatively in terms of components. The developed models could be used to assess the purity of PAMAMs successfully for routine laboratory analysis in future studies.